Reactivity of Diphenylberyllium as a Brønsted Base and Its Synthetic Application

Diphenylberyllium [Be(3)Ph(6)] is shown here to react cleanly as a Brønsted base with a vast variety of protic compounds. Through the addition of the simple molecules tBuOH, HNPh(2) and HPPh(2), as well as the more complex 1,3‐bis‐(2,6‐diisopropylphenyl)imidazolinium chloride, one or two phenyl groups in diphenylberyllium were protonated. As a result, the long‐postulated structures of [Be(3)(OtBu)(6)] and [Be(μ‐NPh(2))Ph](2) have finally been verified and shown to be static in solution. Additionally [Be(μ‐PPh(2))(HPPh(2))Ph](2) was generated, which is only the second beryllium‐phospanide to be prepared; the stark differences between its behaviour and that of the analogous amide were also examined. The first crystalline example of a beryllium Grignard reagent with a non‐bulky aryl group has also been prepared; it is stabilised with an N‐heterocyclic carbene.